WO2015007226A1 - Procédé de préparation d'un mélange composite de dolomite et nouvelle application - Google Patents
Procédé de préparation d'un mélange composite de dolomite et nouvelle application Download PDFInfo
- Publication number
- WO2015007226A1 WO2015007226A1 PCT/CN2014/082428 CN2014082428W WO2015007226A1 WO 2015007226 A1 WO2015007226 A1 WO 2015007226A1 CN 2014082428 W CN2014082428 W CN 2014082428W WO 2015007226 A1 WO2015007226 A1 WO 2015007226A1
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- WO
- WIPO (PCT)
- Prior art keywords
- dolomite
- cement
- portland cement
- concrete
- powder
- Prior art date
Links
- 239000010459 dolomite Substances 0.000 title claims abstract description 177
- 229910000514 dolomite Inorganic materials 0.000 title claims abstract description 177
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000004567 concrete Substances 0.000 claims abstract description 97
- 239000000843 powder Substances 0.000 claims abstract description 72
- 239000003513 alkali Substances 0.000 claims abstract description 49
- 239000002245 particle Substances 0.000 claims abstract description 21
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000004568 cement Substances 0.000 claims description 111
- 239000011398 Portland cement Substances 0.000 claims description 52
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 25
- 239000002893 slag Substances 0.000 claims description 20
- 239000004570 mortar (masonry) Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 239000010881 fly ash Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- 230000002528 anti-freeze Effects 0.000 claims description 7
- 239000004111 Potassium silicate Substances 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 4
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 235000011181 potassium carbonates Nutrition 0.000 claims description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 4
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 4
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- 108010053481 Antifreeze Proteins Proteins 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 2
- 238000007710 freezing Methods 0.000 abstract description 13
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 50
- 238000012360 testing method Methods 0.000 description 49
- 238000006243 chemical reaction Methods 0.000 description 35
- 239000004576 sand Substances 0.000 description 22
- 239000003638 chemical reducing agent Substances 0.000 description 17
- 238000003763 carbonization Methods 0.000 description 13
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 12
- 230000008014 freezing Effects 0.000 description 11
- 238000010586 diagram Methods 0.000 description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 description 10
- 239000011707 mineral Substances 0.000 description 10
- 235000010755 mineral Nutrition 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 238000012423 maintenance Methods 0.000 description 8
- 239000011575 calcium Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 239000011449 brick Substances 0.000 description 5
- 229910052599 brucite Inorganic materials 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000010440 gypsum Substances 0.000 description 5
- 229910052602 gypsum Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 238000010257 thawing Methods 0.000 description 4
- 229910021532 Calcite Inorganic materials 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910019440 Mg(OH) Inorganic materials 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000011083 cement mortar Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- -1 hydroxide ions Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011505 plaster Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010024769 Local reaction Diseases 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 206010036790 Productive cough Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000009862 microstructural analysis Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 210000003802 sputum Anatomy 0.000 description 1
- 208000024794 sputum Diseases 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/026—Comminuting, e.g. by grinding or breaking; Defibrillating fibres other than asbestos
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
Definitions
- the present invention relates to a method for preparing a concrete composite admixture, and more particularly to a method for preparing a dolomite composite admixture and a novel application thereof.
- BACKGROUND OF THE INVENTION It is well known that if dolomite is used as an aggregate in a concrete mix, the dolomite aggregate will react with the alkali in the cement, i.e., alkali-carbonate reaction.
- the alkali-carbonate reaction is a reaction between the alkali in the cement and the dolomite in the coarse aggregate under the condition of water, and causes the local volume expansion of the concrete, which may even cause cracking of the concrete, which is caused by the concrete alkali aggregate.
- the purpose of studying the alkali aggregate reaction is mostly to prevent and inhibit the alkali aggregate reaction from causing damage to concrete engineering.
- ordinary concrete will produce large volume shrinkage due to moisture volatilization, physical and chemical reactions, changes in ambient temperature and humidity, etc., and even cracks may occur due to volume shrinkage. , adversely affecting the load carrying capacity, workability, durability and the like of concrete.
- the product layer of the de-Dolomitization reaction There are K + , Na + and C0 3 2 _ ions, that is, the reaction products K + , Na + and C0 3 2 of the de-Dovamitization reaction do not return to the pore solution, but remain in the product layer to occupy a certain space. Therefore, the space occupied by the dolomitization reaction product is larger than the space occupied by the dolomite participating in the reaction, thereby causing expansion.
- Impervious concrete can generally be made of concrete mixed with an appropriate amount of expansion agent or expanded cement. According to the common types of expansion agents can be divided into: calcium sulphoaluminate, calcium sulphoaluminate - calcium oxide, calcium oxide expansion agent, light burnt magnesium oxide, light burnt dolomite.
- CN102180613A discloses "a steel slag composite powder and a preparation method thereof", which comprises the following raw materials by weight ratio: hot slag steel slag micropowder 30-45, refining slag micropowder 5-10, slag micropowder 30-45, polycarboxylic acid 3-3.5 , triethanolamine 3-3.5, calcium sulfate 5-6, polyaluminum sulfate 4-5 and dolomite powder 2-3.
- the steel slag composite powder can be used in raw materials of cement, concrete and the like to reduce the manufacturing cost of cement, concrete and the like.
- CN101016198 discloses an ultrafine carbonate rock concrete composite admixture and a preparation method thereof, which are composed of ultrafine carbonate rock powder and mineral powder according to 20%-90%: 10%-80% by weight.
- the carbonate rock used is mainly composed of calcite, dolomite or both.
- the carbonate rock is ground into an ultrafine powder and mixed with other mineral powders in proportion.
- the prepared composite admixture can replace 20%-80% cement, reduce the water consumption of concrete, greatly reduce the amount of cement, and formulate high-performance concrete.
- eight copies of the patent literature on dolomite and concrete were found on the website of the State Intellectual Property Office:
- CN1176231 discloses a method for producing "micro-expansion type Portland cement” to produce a fired cement, and dolomite is only one of the raw materials;
- CN1175559 discloses a "micro-expansion, waterproof, crack-resistant colored cement" made of expanded cement mixed with calcined dolomite;
- CN1224633 discloses a "desulfurization method for fluidized bed furnace flue gas" as a desulfurizing agent for a combustion boiler
- CN1631830 discloses a "coal gangue active mixed material, a preparation method thereof and a high performance cement” high temperature calcined dolomite to prepare a coal gangue mixed material
- CN101040017 discloses a "aqueous epoxy resin system” dolomite as a filler for waterborne epoxy resin, which is used for concrete protection;
- CN102776388 A discloses a "Pijiang method for smelting magnesium and application of rare earth oxide as mineralizer" in the form of calcined dolomite, which is mixed into concrete and reacts with water to form a volume expansion effect of magnesium hydroxide. ;
- CN101987761A discloses that "a concentric structure latent flow landscape green space system for deep treatment of small-scale dispersed domestic sewage” is related to sewage treatment, and has nothing to do with building materials such as concrete;
- CN102050614A discloses "a dolomite magnesium cement concrete and a manufacturing method thereof”: dolomite magnesia cement, that is, calcined dolomite and magnesium chloride form magnesium cement;
- CN102092976A discloses an "ecological bulk concrete expansion agent and preparation method" Calcined dolomite is used as an early expansion of concrete to compensate for shrinkage of concrete.
- the above patent documents mostly use dolomite as a raw material to produce calcined dolomite by heating, and use the volume expansion of MgO+H 2 0 ⁇ Mg(OH) 2 to achieve the action of the expansion agent.
- the alkali-carbonate reaction is one of the important types of alkali-aggregate reaction, which causes the concrete to expand in volume, causing cracking of the concrete, causing serious damage to the concrete project and visually It is called "cancer" of concrete.
- the purpose of studying alkali aggregate reaction is to prevent the alkali aggregate reaction from happening, how to effectively inhibit the alkali aggregate reaction, and how to reduce the alkali aggregate reaction caused by concrete engineering. damage.
- the invention is creative in that it overcomes the existing technical prejudice, adopts a technical means that people have abandoned by technical prejudice, and utilizes the volume expansion generated by the alkali carbonate reaction to compensate for the volume shrinkage of the concrete, and obtains a high volume compactness.
- the object of the present invention is to provide a method for preparing a dolomite composite admixture for the deficiencies of the above prior art for improving the durability of concrete.
- Another object of the present invention is to provide a dolomite composite admixture.
- the object of the present invention is achieved by the following technical solutions:
- the preparation method of the dolomite composite admixture mainly comprises the following steps: a. grinding the dolomite to a particle size substantially the same as that of the Portland cement; b.
- dolomite composite admixture When preparing the dolomite composite admixture, mix 2%-20% of dolomite powder according to the quality of the Portland cement, and mix the alkali matter containing ⁇ 1.5% equivalent of sodium oxide according to the mass of dolomite powder. Preparation of dolomite concrete composite admixture. New application of dolomite composite admixture: In the preparation of concrete, 2%-20% alkali dolomite composite admixture is blended according to the quality of Portland cement, which is formulated to have high impermeability, antifreeze and anti-carbonization properties. High durability concrete. Specific experiment: The cement is the Yatai Group P042.5R ordinary Portland cement produced by Yatai Group.
- the equivalent alkali content of the tested cement is about 1.16%, which can be regarded as high alkali cement.
- Dolomite is produced in Shandong.
- the chemical composition of dolomite is: Ca031.41%, Mg021.86%, C0247.73%, and the ratio of Ca 2+ to Mg 2+ is 1:0.69.
- the ratio of Ca 2+ and Mg 2+ was actually measured to be 1:0.67. It was confirmed by X-ray diffractometry to be dolomite, and the dolomite was ground to a particle size by a planetary rapid grinder. According to the provisions of GB/T17671-1999 "Cement mortar strength test method", the test piece is made.
- Each group of test blocks was filled with different levels of dolomite powder, the odd array was cured in air at a temperature of 20 ° C, and the even array was cured in water at a temperature of 20 ° C.
- the amount of change of the test piece was measured on the second day, the fifth day, the tenth day, the seventeenth day, and the twenty-eighth day, and the experimental values are shown in Table 1.
- Schedule 1 the variation of the age of the cement specimens mixed with different dolomite under different curing conditions mm
- the composite admixture concrete member prepared by the invention does not produce cracks, and at the same time improves the impermeability and flexural strength of the concrete, and the actual impermeability level of 28 days reaches the requirement of P14, the process is simple, and the cost is low. It not only improves the performance of the concrete, but also increases the function of the concrete, and the effect is remarkable, which is an unexpected effect.
- Figure 1 is a schematic diagram showing the trend of the linear expansion of the test piece during the curing in air with time
- Figure 2 is a schematic diagram showing the trend of the linear expansion of the test piece during the maintenance of water in time
- FIG. 4 is a schematic diagram of the scanning electron microscope test results of adding 5% dolomite and curing the test piece in the air, wherein no obvious Micro-cracks;
- Figure 5 is a schematic diagram of the results of adding 5% dolomite specimens and blank specimens after 150 freeze-thaw cycles, in which 5% dolomite specimens were not damaged, and the blanks were frozen at 150 times.
- Figure 6 is a schematic diagram of the results of scanning electron microscopy of the sample numbered 1# in Schedule 5, showing microscopic cracks;
- Figure 7 is the sample numbered 11# in Schedule 5.
- Another object of the present invention is to provide a dolomite composite admixture for Portland cement, the dolomite composite admixture comprising dolomite powder and an alkali metal compound, and the fineness of the dolomite powder satisfies the Portland cement
- the fineness standard, the molar ratio of the alkali metal ion of the alkali metal compound to the dolomite powder is ⁇ 2:1.
- the particle size of the dolomite powder in the above dolomite composite admixture is equivalent to the particle size of the Portland cement. Therefore, when it is used as a composite admixture of Portland cement, dolomite powder and alkali generate so-called alkali aggregate in the art.
- CaMg (C0 3 ) 2 + 2MOH CaC0 3 +Mg(OH) 2 +M 2 C0 3
- M is an alkali metal ion: Na + , K + , Li + .
- the hydroxide ions consumed in the above reaction are from Portland cement, and the corresponding alkali metal ions may be derived from alkali metal compounds or from Portland cement. When the Portland cement contains less alkali metal oxides.
- the amount of the alkali metal compound in the dolomite composite admixture of the present invention can be appropriately adjusted; it will be apparent to those skilled in the art that the alkali metal ion (M + ) can be reused and dolomite in the above alkali aggregate reaction.
- the action of MgC0 3 , and its content will affect the progress of the alkali aggregate reaction, so those skilled in the art can use the above reaction principle according to the actual needs, the molar ratio of alkali metal ions to dolomite powder is less than 2:1.
- the amount of the alkali metal compound is adjusted.
- the expansion effect of the reaction is used to compensate the volume shrinkage of the concrete, so that the concrete having the volume is high in density; in addition, the magnesium hydroxide formed by the above reaction, that is, the brucite, can make the micropores of the Portland cement.
- the filling is dense, which increases the resistance of the cement to the liquid flow.
- the brucite colloid has a large specific surface area and good hydrophilicity, it preferentially adsorbs the OH-ion to make the brucite colloid negatively charged and can The hydrated counterion in the molecule and the solution is bound in the colloidal flocculation structure. At this time, the water in the pore is no longer the free water of common nature, but the water molecules are arranged in an orderly manner. According to the capillary, the capillary is finer. The principle that the freezing point of water is larger, and the freezing point of the cationic solution containing Na + , K + and the like is lower, so that the water in the inner hole of the concrete and the cement product having the above dolomite composite admixture is at a low temperature condition.
- the above dolomite powder is a powder of C a Mg(C0 3 ) 2 which is understood by those skilled in the art, and may be derived from a dolomite chemical product obtained by purification treatment or a dolomite containing dolomite directly, regardless of The dolomite products are also dolomite, which can all achieve the above effects.
- the alkali metal compound which can be used in the present invention may be an inorganic alkali metal compound which is commonly used in the art, for example, the alkali metal compound is selected from the group consisting of sodium oxide, sodium hydroxide, sodium silicate, sodium carbonate, sodium hydrogencarbonate, sodium sulfate, potassium oxide, One or more of the group consisting of potassium hydroxide, potassium silicate, potassium carbonate, potassium sulfate, lithium oxide, lithium hydroxide, lithium silicate, lithium carbonate, and lithium sulfate.
- the above alkali metal compounds are capable of forming MOH in the environment of Portland cement, and further providing alkali ions for the alkali aggregate reaction of dolomite.
- Another object of the present invention is to provide a cement comprising Portland cement and dolomite powder.
- the amount of dolomite powder is 2-28% by weight, preferably 2-20% by weight of the Portland cement, and the fineness of the dolomite powder is satisfied.
- the Portland cement of the present application is the same as the Portland cement in the prior art, and generally has an alkali metal compound. According to the above description, the alkali ions corresponding to the alkali metal ions in the dolomite powder and the Portland cement occur.
- the alkali aggregate reaction increases the compactness of the concrete and improves the impermeability, frost resistance and carbonation resistance of concrete and cement products.
- the dolomite powder used in the above cement is a powder of CaMg(C0 3 ) 2 which is understood by those skilled in the art, and may be derived from a dolomite chemical product obtained by purification treatment, or may be directly used to contain dolomite. Dolomite, whether using dolomite products or dolomite, can achieve the above effects.
- the dolomite powder is taken from dolomite having a dolomite content of 70 to 99% by weight, and the dolomite powder is used in an amount of 3 to 12% by weight of the Portland cement.
- the above cement further includes an alkali metal compound, and a part of the alkali metal compound is carried by the acid salt cement to control the alkali of the alkali metal compound.
- the molar ratio of the metal ion to the dolomite powder is ⁇ 2: 1, as described above, the alkali metal ion can repeatedly react with the residual dolomite alkali aggregate, and therefore, the amount of the alkali metal compound in the cement of the present invention is controlled as described above.
- the scope can meet the requirements of enhancing the impermeability, frost resistance and carbonization resistance of cement products.
- the molar ratio of the above alkali metal ion to dolomite powder is ⁇ 1:1, more preferably ⁇ 1:3, more preferably ⁇ 1:10.
- the alkali metal compound used in the present invention may be an inorganic alkali metal compound commonly used in the art, such as an alkali metal compound selected from the group consisting of sodium oxide, sodium hydroxide, sodium silicate, sodium carbonate, sodium hydrogencarbonate, sodium sulfate, potassium oxide, One or more of the group consisting of potassium hydroxide, potassium silicate, potassium carbonate, potassium sulfate, lithium oxide, lithium hydroxide, lithium silicate, lithium carbonate, and lithium sulfate.
- the above alkali metal compounds are capable of forming MOH in the environment of Portland cement, and further providing alkali ions for the alkali aggregate reaction of dolomite.
- the above-mentioned Portland cement as one of the raw materials is selected from pure cement Portland cement, ordinary Portland cement, slag Portland cement, pozzolan Portland cement, fly ash Portland cement and composite silicate.
- Still another object of the present invention is to provide an application of the above cement in mortar or concrete. When the cement of the present invention is applied to mortar or concrete, the anti-freezing, impermeability and anti-carbonization properties of the mortar and concrete can be effectively optimized.
- Example 1 Anti-cracking mortar The plaster was composed of PC 32.5 cement: medium sand of 1:3 and an appropriate amount of water, and incorporated 10% by weight of dolomite powder and 0.2% sodium carbonate. Specifically: 370 kg of cement, 1350 kg of medium sand, 37 kg of dolomite powder, 0.037 kg of sodium carbonate. On the red brick clear water wall, the surface of the square was 1 square meter with mortar, and after 7 days, no crack was found in the mortar surface. Also on the red brick clear water wall, the comparative plastering mortar without the dolomite powder is also coated with three pieces of 1 square meter in size. After 7 days, there are fine mortar cracks.
- Impervious concrete C30P6 pumped impervious concrete reference ratio: P042.5 strength grade cement, cement alkali content 0.85%, cement dosage 275kg, fly ash 80kg, medium sand 840kg, gravel 5 ⁇ 31.5mm
- the particle size is 1010kg, water is 170kg, and naphthalene-based water reducing agent is 9kg.
- the 28-day actual detection of the impermeability level reached the P8 requirement.
- C30P6 pumped impervious concrete test ratio P042.5 strength grade cement, cement dosage 275kg, fly ash 40kg, dolomite concrete composite admixture 40kg, including sodium hydroxide 0.24 kg, sand 836kg, gravel 5 ⁇ 31.5mm particle size 1008 kg, water 170kg, water reducing agent 9kg.
- the 28-day actual impermeability rating is up to P10.
- Experimental dolomite composite mineral admixture composed of 40% fly ash, 39.5% dolomite powder, 0.5% sodium hydroxide and 20% slag powder.
- C30 concrete reference mix ratio P042.5 strength grade cement, cement dosage 278kg, reference compound blending 1450 kg, sand 830kg, gravel 5 ⁇ 31.5mm particle size 1080 kg, water 168kg, water reducing agent 5.4kg.
- C30 concrete experimental mix ratio P042.5 strength grade cement, cement dosage 278kg, dolomite composite admixture 50 kg, sand 830kg, gravel 5 ⁇ 31.5mm particle size 1080 kg, water 168kg, water reducing agent 5.4kg.
- the 28-day compressive and flexural strength of concrete is shown in Table 4. From the experimental results, it can be seen that the dolomite composite admixture also has the effect of improving the flexural strength of concrete.
- Example 4 Reference composite mineral admixture: consisting of 60% fly ash and 40% slag powder.
- Dolomite composite mineral admixture 40% of fly ash, 39.5% of dolomite powder, 1.2% of sodium dolomite powder, 20% of slag powder.
- C30P6 pumped impervious concrete blank test mix ratio P042.5 strength grade cement, cement alkali content 0.85%, cement dosage 278kg, reference composite admixture 80 kg, sand 830kg, gravel (5-31.5mm) 1080 Kg, water 168kg, naphthalene high-efficiency water reducing agent 9kg. After 28 days, the slow freezing method was used to detect freezing and thawing 100 times.
- Example 5 Cement is the Dinglu P042.5R ordinary Portland cement produced by Yatai Group.
- the equivalent alkali content of the tested cement is about 1.16%, which can be regarded as high alkali cement.
- the fineness of the cement is 0.045mm square hole.
- the sieve residue of the sieve was 15% by weight.
- the experimental results can be seen from the attached table 5.
- the dolomite-doped samples mixed with high-alkali cement are cured, and the specimens are slightly expanded.
- the number of specimens cured in water is larger than that in air.
- Analytical comparison, scanning electron microscopy detection of two samples of dolomite air-free curing test piece and adding 5wt% dolomite air-maintenance test piece, the test results are shown in Figure 6 and Figure 7, from Figure 6 and Figure
- the microstructure analysis of the scanning electron microscope of 7 shows that the micro-cracks of the cement stone added with dolomite are significantly reduced;
- FIG. 8A and FIG. 8B show the 200 pieces of slow freezing and freezing of the blank test piece and the test piece added with 6wt% dolomite.
- FIG. 8A shows that the blank sample showed significant freezing damage after 200 freeze-thaw cycles
- FIG. 8B showed that the test piece added with 6% dolomite was not damaged. It can be seen that the composite admixture concrete member prepared by the invention does not produce cracks, and at the same time improves the impermeability and flexural strength of the concrete. In addition, the actual impermeability level of the 28-day test reaches the requirement of P14.
- Example 6 and Example 7 The test of applying the cement of the present invention to a mortar:
- Example 6 Anti-cracking mortar The plaster is composed of PC32.5 cement and medium sand in a ratio of 1:3, and is doped with 10% by weight of dolomite powder (dolomite content 99wt%) and 0.2% sodium carbonate. For: 370 kg of cement, 1350 kg of medium sand, 37 kg of dolomite powder, 0.037 kg of sodium carbonate. On the red brick clear water wall, use a mortar to wipe the surface of 1 square meter and see three pieces. After 7 days, the mortar was tested and no cracks were found. Also on the red brick clear water wall, the comparative plastering mortar without dolomite powder (the same as the dolomite powder is the same as the plastering mortar). It also covers three square meters of 1 square meter.
- Example 7 Raw materials: Liaoyuan Jingang Cement Group produces cement clinker, tested for 3 days strength 27.6MPa, 28 days strength 57.6MPa, cement clinker equivalent alkali content 1.2 wt%; Jilin Tonghua Liuhe gypsum, S0 3 content 25%; The Changchun Thermal Power Plant II produces fly ash; Tonggang produces slag powder, Liaoning dolomite, which is confirmed by energy spectrometer and X-ray diffractometer to be dolomite, and the effective dolomite content is 96wt%.
- Example 8 to Example 12 The test of applying the cement of the present invention to concrete: The dolomite powder is from the dolomite produced in Liaoning, and is confirmed to be dolomite by energy spectrometer and X-ray diffractometer, and the content of dolomite is 96wt%.
- C30P6 pumped impervious concrete 1 P042.5 strength grade cement, cement alkali content 0.85%, cement dosage 278kg, reference composite admixture 80 kg, sand 830kg, crushed stone (particle size 5 ⁇ 31.5mm) 1080 kg, water 168kg, naphthalene-based high-efficiency water reducing agent 9kg
- the freeze-thaw method of GB/T50082-2009 is used to test the freezing and thawing 100 times.
- the actual impermeability level can reach P8.
- C30P6 pumped impervious concrete II P042.5 strength grade cement, cement alkali content 0.88%, cement dosage 278kg, dolomite composite admixture 80 kg, sand 830kg, particle size 5 ⁇ 31.5mm gravel 1080 kg, 168kg of water, 9.2kg of naphthalene-based high-efficiency water reducing agent.
- the freeze-thaw method was tested for 200 times after 28 days, and the actual impermeability level after 28 days was up to P14.
- C20 concrete reference ratio PC32.5 general Portland cement, cement alkali content 1.1%, cement dosage 302kg, particle size 5 ⁇ 31.5mm gravel 1238kg, sand 625 kg water 175kg, naphthalene water reducer 9.1 Kg. After standard maintenance, the actual impermeability level is up to P6 after 28 days.
- C20 concrete test ratio PC32.5 high durability cement (12% by weight of dolomite, 53wt% of sputum, 17wt% of gypsum, 17wt% of fly ash, 12wt% of slag powder, lwt% of sodium sulphate), 302kg of cement, 625kg of sand , 1238 kg of gravel with a particle size of 5 ⁇ 31.5mm, 175kg of water, and 9.1kg of naphthalene-based water reducing agent. After standard maintenance, the actual impermeability level is up to P12 after 28 days.
- C30P6 pumped antifreeze concrete foundation mix ratio general silicate P042.5 strength grade cement, cement dosage 325kg, medium sand 835kg, particle size 5 ⁇ 31.5mm gravel 1010kg, water 170kg, naphthalene water reducer 9 kg, made of 100 X 100 X 100mm cubic concrete specimens, after 28 days of standard curing, the concrete specimens were tested for freeze-thaw resistance up to 100 times.
- C30P6 pumped antifreeze concrete test mix ratio P042.5 high durability cement (Dolomite 8wt%, dip
- Example 11 C30 concrete reference ratio: P042.5 strength grade cement, cement alkali content 0.88%, cement dosage is
- the concrete carbonation test method of GB/T50082-2009 is used in the test method for long-term performance and durability test of ordinary concrete.
- the actual carbonization depth of concrete specimens after standard curing for 28 days is 8.7 mm.
- the concrete carbonation test method of GB/T50082-2009 is used in the test method for long-term performance and durability of ordinary concrete.
- the average carbonization depth of concrete specimens after 28 days of standard curing is 4.5 mm.
- C20 concrete reference ratio PC32.5 general Portland cement, cement alkali content 1.1%, cement dosage 302kg, particle size 5 ⁇ 31.5mm gravel 1238kg, sand 625 kg water 175kg, naphthalene water reducer 9.1 Kg. 28 Tianjing carbonization box carbonization experiment, the actual detection of the average carbonization depth of 9.3mm.
- C20 concrete test ratio PC32.5 high durability cement (Dolomite 12wt%, 53 53wt%, gypsum
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Abstract
L'invention concerne un procédé de préparation d'un mélange composite de dolomite et une nouvelle application ; le procédé de préparation d'un mélange composite de dolomite comprend : la lévigation de la dolomite en particules basiquement identiques à celles du béton silicaté ; l'addition d'une proportion spécifique de poudre de dolomite par masse de béton silicaté ; l'addition d'une quantité équivalente spécifique d'une substance contenant un métal alcalin d'oxyde de sodium par masse de poudre de dolomite et le mélange uniforme pour préparer un mélange composite de béton présentant des performances d'imperméabilité. Un béton présentant des caractéristiques anticongélation et d'imperméabilité et une résistance élevée à la flexion peut être préparé par l'addition d'un mélange composite de dolomite par masse de béton silicaté lors de la préparation de béton de durabilité élevée.
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